Herbicidal meta-bifunctional benzenes

ABSTRACT

Novel compounds and their herbicidal use having the formula ##STR1## wherein A is selected from the group ##STR2##

This is a division of application Ser. No. 549,128 filed Feb. 11, 1975,now U.S. Pat. No. 4,013,450, which is a division of application Ser. No.77,677 filed Oct. 2, 1970, now U.S. Pat. No. 3,867,426.

This invention relates to novel meta-bifunctional substituted benzenes.This invention further relates to herbicidal compositions and methods ofherbicidal use utilizing the novel meta-bifunctional substitutedbenzenes of this invention.

The novel meta-bifunctional substituted benzenes of this invention areof the formula ##STR3## wherein Z¹ is selected from the group consistingof oxygen and sulfur; R¹ is selected from the group consisting ofhydrogen, alkyl having a maximum of 8 carbon atoms and alkenyl having amaximum of 6 carbon atoms; R² is selected from the group consisting ofhydrocarbyl selected from the group consisting of alkyl, alkenyl,alkynyl and cycloalkyl said alkyl, alkenyl and alkynyl having a maximumof 12 carbon atoms and said cycloalkyl having 3 to 7 ring carbon atomsand a maximum of 4 chain carbon atoms, alkoxy having a maximum of 6carbon atoms, chloroalkyl having a maximum of 6 carbon atoms and amaximum of 3 halogen atoms, chloroalkenyl having a maximum of 6 carbonatoms and a maximum of 3 halogen atoms, cycloalkenyl having 5 to 7 ringcarbon atoms and a maximum of 4 chain carbon atoms, phenyl, substitutedphenyl having a maximum of two substituents said substituents beingselected from the group consisting of halogen, nitro and alkyl having amaximum of 4 carbon atoms, the group ##STR4## wherein R⁴ and R⁵ are eachindependently selected from the group consisting of hydrogen, alkylhaving a maximum of 12 carbon atoms, alkenyl having a maximum of 3carbon atoms, chloroalkyl having a maximum of 3 carbon atoms and amaximum of 3 halogen atoms, chloroalkenyl having a maximum of 3 carbonatoms and 3 halogen atoms; R⁶ is selected from the group consisting ofhalogen, alkyl having a maximum of 14 carbon atoms, chloroalkyl having amaximum of 3 carbon atoms and a maximum of 3 halogen atoms, nitro, andalkoxy having a maximum of 3 carbon atoms; and r is one of the integerszero to three; the group ##STR5## wherein R⁷ is selected from the groupconsisting of alkyl and alkenyl each having a maximum of 4 carbon atoms,and R⁴, R⁵, R⁶ and r are as previously defined; and R³ is selected fromthe group consisting of hydrogen, alkyl having a maximum of 12 carbonatoms, and alkenyl having a maximum of 8 carbon atoms, R² and R³ canwith the nitrogen form the group selected from the group consisting of##STR6## provided that when R² or R³ is unsaturated the position ofunsaturation is other than on the 1-carbon atom;

wherein R⁸ is alkyl having a maximum of 3 carbon atoms and s is one ofthe integers zero to two;

A is selected from the group consisting of ##STR7## wherein Z² and Z³are independently selected from the group consisting of oxygen orsulfur; R⁹ is selected from the group consisting of hydrocarbyl selectedfrom the group consisting of alkyl, alkenyl, alkynyl and cycloalkyl saidalkyl, alkenyl and alkynyl having a maximum of 12 carbon atoms and saidcycloalkyl having 3 to 7 ring carbon atoms and a maximum of 4 chaincarbon atoms, chloroalkyl having a maximum of 15 carbon atoms and amaximum of 3 halogen atoms, chloroalkenyl having a maximum of 12 carbonatoms and a maximum of 3 halogen atoms and alkoxyalkyl having a maximumof a total of 12 carbon atoms, the group --CH₂ (CH₂)_(x) OR¹⁷ wherein xis one of the integers zero to four and R¹⁷ is selected from the groupconsisting of phenyl, naphthyl, substituted phenyl and substitutednaphthyl said substitution being a maximum of 3 substituents and saidsubstituent being independently selected from halogen and alkyl having amaximum of 4 carbon atoms, --CH₂ CH═CH--phenyl, the group ##STR8##wherein R¹¹ is selected from the group consisting of phenyl and naphthyland R⁴, R⁵, R⁶, R⁷ and r are as previously defined; R¹⁰ is selected fromthe group consisting of hydrogen, alkyl having a maximum of 12 carbonatoms, cycloalkyl having 5 to 7 carbon atoms, alkenyl having a maximumof 4 carbon atoms, chloroalkyl having a maximum of 6 carbon atoms and amaximum of 3 halogen atoms and chloroalkenyl having a maximum of 4carbon atoms and a maximum of 3 halogen atoms; provided that when R² isa hydrocarbyl group having less than 9 carbon atoms then R⁹, when ahydrocarbyl group, has at least 8 carbon atoms; ##STR9## wherein Z⁵ andZ⁶ are each independently selected from the group consisting of oxygenand sulfur; R¹² is selected from the group consisting of hydrogen, alkylhaving a maximum of 6 carbon atoms and alkenyl having a maximum of 6carbon atoms; and R¹³ is selected from the group consisting of alkylhaving a maximum of 8 carbon atoms, alkenyl having a maximum of 6 carbonatoms, cycloalkyl having from 3 to 7 ring carbon atoms, cyclohexenyl,phenyl, substituted phenyl having a maximum of two substituents saidsubstituents being selected from the group consisting of halogen, nitroand alkyl having a maximum of 4 carbon atoms, the group ##STR10##wherein R⁴, R⁵, R⁶, R⁷ and r are as previously defined; and ##STR11##wherein Z⁶ is selected from the group consisting of oxygen and sulfur;

R¹⁴ is selected from the group consisting of hydrogen, alkyl having amaximum of 8 carbon atoms and alkenyl having a maximum of 6 carbonatoms; R¹⁵ is selected from the group consisting of alkyl having amaximum of 12 carbon atoms, alkenyl having a maximum of 7 carbon atoms,alkoxy having a maximum of 6 carbon atoms, chloroalkyl having a maximumof 6 carbon atoms, and a maximum of 3 halogen atoms, chloroalkenylhaving a maximum of 6 carbon atoms and a maximum of 3 halogen atoms,cycloalkyl having 3 to 7 ring carbon atoms and a maximum of 4 chaincarbon atoms, cycloalkenyl having 5 to 7 ring carbon atoms and a maximumof 4 chain carbon atoms, phenyl, substituted phenyl having a maximum oftwo substituents said substituents being selected from the groupconsisting of halogen, nitro and alkyl having a maximum of 4 carbonatoms, ##STR12## wherein R⁴, R⁵, R⁶, R⁷ and r are as previously defined;and R¹⁶ is selected from the group consisting of hydrogen, alkyl havinga maximum of 12 carbon atoms and alkenyl having a maximum of 8 carbonatoms; R¹⁵ and R¹⁶ can with the nitrogen form the group selected fromthe group consisting of ##STR13## wherein R⁸ and s are as previouslydefined.

A preferred embodiment of this invention are the compounds wherein onlyone of R⁴ and R⁵ is alkenyl or chloroalkenyl and that R⁷ is other thanalkenyl when either R⁴ or R⁵ is alkenyl or chloroalkenyl.

Another preferred embodiment of this invention is the class of compoundsof the formula ##STR14## wherein R¹, R², R³, R⁹, R¹⁰, Z¹ and Z³ are aspreviously defined in the above preferred embodiment.

Within this class of compounds preferred embodiments are those compoundsin which R¹ is hydrogen or alkyl having a maximum of 4 carbon atoms.

A further embodiment, within this class, are those compounds in which R¹is hydrogen and R² is selected from the group consisting of chloroalkylhaving a maximum of 6 carbon atoms and a maximum of 3 halogen atoms,chloroalkenyl having a maximum of 6 carbon atoms and a maximum of 3halogen atoms, ##STR15## wherein R³, R⁴, R⁵, R⁶, R⁷, R⁹, R¹⁰, Z³ and rare as previously defined.

A still further embodiment, within this class, are those compounds inwhich R¹ is hydrogen, R⁹ is selected from the group consisting ofchloroalkyl having a maximum of 12 carbon atoms and a maximum of 3halogen atoms, chloroalkenyl having a maximum of 8 carbon atoms and amaximum of 3 halogen atoms, --CH₂ CH═CH--phenyl and the group ##STR16##wherein R², R³, Z¹, Z³, Z⁴, R⁵, R⁶, R⁷, R¹¹ and r are as previouslydefined; and R¹⁰ is selected from the group consisting of hydrogen,alkyl having a maximum of 12 carbon atoms, cycloalkyl having 5 to 7 ringcarbon atoms, alkenyl having a maximum of 4 carbon atoms, chloroalkylhaving a maximum of 6 carbon atoms and a maximum of 3 halogen atoms andchloroalkenyl having a maximum of 4 carbon atoms and a maximum of 3halogen atoms.

Another preferred embodiment of this invention are the compounds of theformula ##STR17## wherein R¹ is selected from the group consisting ofhydrogen and alkyl having a maximum of 4 carbon atoms; and R¹² isselected from the group consisting of hydrogen and alkyl having amaximum of 4 carbon atoms; and R², R³, Z¹, Z⁴ and R⁵ are as previouslydefined in the preferred embodiment.

Another embodiment, within this class, are those compounds in which R¹and R¹² are both hydrogen.

A still further embodiment of this invention are those compounds of theformula ##STR18## wherein R¹ and R¹⁴ are each independently selectedfrom the group consisting of hydrogen and alkyl having a maximum of 4carbon atoms; and R², R³, R¹⁵, R¹⁶, Z¹ and Z⁶ are as previously definedin the preferred embodiment.

The meta bifunctional compounds of this invention can be prepared by aprocess represented by the following equation: ##STR19## wherein Y isSH, OH or NO₂ ; X is chloro or bromo; and R¹, R² and R³ are aspreviously defined.

When Y is hydroxy or mercapto the following synthesis represents a modeof preparations of the desired compounds: ##STR20## wherein R¹, R², R³,R⁹, R¹⁰, Z³ and X are as previously defined.

When Y is nitro the following synthesis represents a mode of preparationof the desired compounds: ##STR21## wherein R¹, R², R³, R¹², R¹³, R¹⁴,R¹⁵, R¹⁶, Z¹, Z⁴, Z⁵, Z⁶ and X are as previously defined.

The above reactions are represented equations as to modes of preparationof the desired compounds. Other modes are available and are listed inthe literature and the following examples.

The starting nitroanilines or hydroxyanilines are commercially availableor are easily prepared by known methods.

Hydrogenation of the nitro group may be by any of the procedures knownto those skilled in the art, such as catalytic hydrogenation; metal-acidcombinations such as iron-acid; metal-alcohol combinations such as zincdust or aluminum amalgams and aqueous alcohol; lithium aluminum hydrideand the like.

The procedure used may depend upon the groups already present on thering. These procedures are also well known to those skilled in the art.A preferred procedure is catalytic hydrogenation utilizing 5% palladiumon charcoal.

In the above reaction sequences it is not required that the urea groupmay be formed first. The second group may be formed first followed byhydrogenation of a nitro group and formation of the urea group. Theactual method used depends upon convenience and nature of the group tobe formed. This will be illustrated in the examples showing thepreparation of some of the starting compounds from which the ureafunction is then formed as illustrated in the equations.

The above reaction equation shows the interrelationship of the threegroups of compounds. The reactions, starting compounds, intermediatesand/or reactants to form each group are common to the groups.

It will be shown hereinafter that this interrelationship of the groupsalso extends to their herbicidal activity.

The following examples will illustrate the invention. In the followingexamples as well as in the specification and appended claims, parts andpercent are by weight unless otherwise indicated.

EXAMPLE 1

This example describes the preparation of3-(3'-hydroxyphenyl)-1,1-dimethylurea.

To a suitable vessel charged with 343.5 parts m-aminophenol in 1800parts ethyl acetate was added 187 parts dimethylcarbamoyl chloride andthe resultant mixture stirred at room temperature for 15 hours. To thismixture was then added 177 parts triethylamine and the mixture stirredfor 6 hours. Dimethylcabamoyl chloride (187 parts) was then added andthe resultant mixture stirred 72 hours at room temperature. The solidwhich separated was filtered and washed with ethyl acetate and thenwater and then air dried. mp 199.5°-201° C.

EXAMPLE 2

This example describes the preparation of1,1-dimethyl-3-[3'-(N-alpha-methylbenzylcarbamoyloxy)phenyl] urea.

To a suitable vessel charged with 44.4 parts tetrahydrofuran, 23.6 partsdimethylformamide and 1.45 parts triethylamine was added, with stirring,18 parts 1,1-dimethyl-3-(3'-hydroxyphenyl)urea. To the resultant mixturewas added, with stirring, 16.2 parts alpha-methylbenzyl isocyanate. Thesolution was stirred at about 35° C. for 2 hours and then left standingat room temperature for about 15 hours. A solution of ethyl ether-hexane(128.5 parts ethyl ether and 79.1 parts n-hexane) was added to themixture, with stirring, and then filtered and the crystals washed withethyl ether and dried. mp 167°-168° C.

Analysis for C₁₈ H₂₁ N₃ O₃ : Calc'd: C, 66.06; H, 6.47; N, 12.84. Found:C, 66.24; H, 6.36; N, 12.67.

EXAMPLE 3

This example describes the preparation of 1,1-dimethyl-3-[3'-(n-alphat-butyl-4-methoxybenzylcarbamoyloxy)phenyl]urea.

This example follows the procedure of Example 2 substituting 24.01 partsof alpha t-butyl-4-methoxybenzyl isocyanate for the alpha methylbenzylisocyanate. The product, recrystallized from methanol-water, melted215°-217° C.

Analysis for C₂₂ H₂₉ N₃ O₄ : Calc'd: C, 66.14; H, 7.32; N, 10.52. Found:C, 66.21; H, 7.32; N, 10.63.

EXAMPLE 4

This example describes the preparation of1-(2-chloroallyl)-1-dodecyl-3-[3'-(N-methylcarbamoyloxy)phenyl]urea.

To a suitable vessel charged with 245 partsm-hydroxyphenylisothiocyanate and 450 parts ethyl acetate was added,with stirring, 3.6 parts triethylamine and then, over about a 1/2 hourperiod, 114 parts methyl isocyanate. The reaction temperature increasedto about 60° C. The resultant mixture was stirred for about 30 minutes,cooled and 330 parts n-hexane added during which time crystals separatedfrom solution. To the mixture was then added 390 parts of a solution,containing 225 parts ethyl acetate and 165 parts n-hexane, and themixture cooled to 5° C. The mixture was filtered and the crystals,m-(N-methylcarbamoyloxy)phenylisocyanate washed with an ethylacetate-n-hexane (2:3 volivol) solution mp 98°-99° C.

To a suitable vessel charged with 4.2 partsm-(N-methylcarbamoyloxy)phenylisocyanate was added 5.3 partsN-(2-chloroallyl)dodecylamine in 16 parts methanol. The resultantmixture was heated to about 60° C. and then water added until themixture turned cloudy. The resultant mixture was then allowed to stand,overnight, at room temperature. The ether was then removed yielding theproduct, mp 112°-113° C.

Analysis for C₂₄ H₃₈ ClN₃ O₂ S: Calc'd: N, 8.98; S, 6.85. Found: N,9.18; S, 6.95.

EXAMPLE 5

This example describes the preparation of1,1-dimethyl-3-[3'-(3"-(2-phenoxyethyl)ureido)phenyl] urea of theformula ##STR22##

To a suitable vessel charged with 17.92 parts1,1-dimethyl-3-(m-aminophenyl)urea, 23.6 parts dimethylformamide, 44.4parts tetrahydrofuran and 0.363 parts triethylamine was added, withstirring, 16.32 parts 2-phenoxyethylisocyanate (prepared from2-phenoxyethylamine and phosgene), and the resultant mixture stirred forabout 2 hours. Ethyl ether, 286 parts, was then added during which timea precipitate started to form. The mixture was allowed to standovernight, then filtered and the solid washed with ethyl ether and airdried. mp 133°-136° C.

Analysis for C₁₈ H₂₂ N₄ O₃ : Calc'd: C, 63.14; H, 6.48; N, 16.36. Found:C, 63.31; H, 6.70; N, 16.31.

EXAMPLE 6

This example describes the preparation of 1,1-dimethyl-3-[3'-(3"-(alpha,4-dimethyl-benzyl)ureido)phenyl] urea of the formula ##STR23##

This example is similar to Example 5, substituting 16.12 partsalpha,4-dimethylbenzylisocyanate for the 2-phenoxyethylisocyanate,yielding the product melting 203°-205° C.

Analysis for C₁₉ H₂₄ N₄ O₂ : Calc'd: C, 67.03; H, 7.11; N, 16.46. Found:C, 67.25; H, 7.19; N, 16.49.

EXAMPLE 7

This example describes the preparation of3-[3'-(N,alpha,4-dimethylbenzyl-N-methylcarbamoyloxy)phenyl]-1,1-dimethylurea.

To a suitable vessel charged with 60 parts sodium methoxide and 633parts methanol was added, with stirring, a solution consisting of 180parts 1,1-dimethyl-3-(m-hydroxyphenyl) urea and 802 parts methanol. Theresultant mixture was stirred and the methanol removed under reducedpressure until a dry solid was obtained. The solid, sodium salt of1,1-dimethyl-3-(m-hydroxyphenyl) urea, was washed with benzene.

To a suitable vessel charged with 17.4 parts sodium salt of1,1-dimethyl-3-(m-hydroxyphenyl) urea (prepared above) and 57.95 partsacetonitrile was added with stirring 12.7 partsN-methyl-N-alpha,4-di-methylbenzylcarbamoyl chloride and the mixturestirred about 2 hours at room temperature and then let stand for about 2days at room temperature. The solvent was then removed under reducedpressure and the residue dissolved in toluene. The toluene solution wasextracted with water, dried and concentrated. The resultant oil wastaken up in xylene from which the product, as a solid was obtained, mp113°-116° C. Analysis for C₂₀ H₂₅ N₃ O₃ : Calc'd: C, 67.58; H, 7.09; N,11.82. Found: C, 67.74; H, 7.16; N, 11.72.

EXAMPLE 8

This example describes the preparation of methyl m-aminocarbanilate.

To a suitable vessel charged with 500 parts m-nitroaniline, 315 partspotassium carbamate, 800 parts water, 800 parts ice and 901 parts ethylacetate was added, with stirring, 380 parts methyl chloroformate overabout a 2 hour period, white maintaining the reaction temperature atbelow about 15° C. Hexane (330 parts) was then added and the resultantmixture stirred about 2 hours at 25° to 30° C. The mixture was thenfiltered and the solid washed with a 1:1 mixture of n-hexane-ethylacetate, then with water and dried. The product-methylm-nitrocarbanilate-melted at 148°-150° C.

To a suitable hydrogenation apparatus was charged 664 parts methylm-nitrocarbanilate, 9 parts palladium on carbon and 1241 parts dioxane.The apparatus was then purged and pressurized to 800 psi with hydrogen.On agitation, the temperature rose slowly to about 80° C. and thendropped and the pressure dropped to 0 psi. The temperature ws about 50°C. when the pressure was 0 psi. The apparatus was repressurized to 500psi and the temperature rose to 85° C. Process was repeated until nopressure drop or temperature rise was noted. The mixture was agitated inthe system for an additional hour, and then the apparatus vented and themixture filtered. The solvent was removed under reduced pressure until apot temperature of 80° C./0.2 mm pressure was obtained. The oil whichwas obtained crystallized on standing--mp 67°-69° C. Recrystallizationfrom methanol and then ethyl acetate-toluene-methylcyclohexane yieldedthe product melting 71°-71.5° C.

EXAMPLE 9

This example describes the preparation of methylm-(3-t-butylureido)carbanilate of the formula ##STR24##

A suitable vessel was charged with 16.6 parts methyl m-aminocarbanilate,prepared in Example 8, 88.8 parts tetrahydrofuran, 14.9 partst-butylisocyante and 0.73 parts triethylamine and the resultant mixturerefluxed for about 8 hours. To the hot mixture was added 132 partsn-hexane and the mixture allowed to cool overnight. The solvent wasremoved under reduced pressure and the solid residue stirred with 300parts of a 4% hydrochloric acid solution. The mixture was filtered andthe solid washed with water. The solid product was recrystallized frommethanol. mp 145°-147° C.

EXAMPLE 10

This example describes the preparation of methylm-[3-(1,1,3,3-tetramethylbutyl)ureido] carbanilate of the formula##STR25##

The process of Example 9 was followed substituting 21 parts1,1,3,3-tetramethylbutylisocyanate for 14.9 parts t-butylisocyanate. Theproduct melted at 152°-153° C.

The following carbamoyloxyureas were prepared by substantially the sameprocedure as previously shown. In the naming of the compounds a C═S inthe urea group is referred to as thiourea. Replacement of sulfur foroxygen in the carbamoyloxy group will be named as follows: ##STR26## Thenitrogen of the urea group attached to the meta-bifunctional phenyl willbe the 3-position nitrogen. The nitrogen of the carbamoyloxy group willbe indicated as "N".

3-[3'-(N'-3,4-dichlorophenylcarbamoyloxy)phenyl]-1-(3,4-dichlorophenyl)urea

3-[3'-(N'-methylcarbamoyloxy)phenyl]-1-(2-chloroallyl)-2-thiourea

3-[3'-(N'-alpha-methylbenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-alpha-methylbenzylcarbamoyloxy)phenyl]-1-tert-butyl-2-thiourea

3-[3'-(N'-methylcarbamoyloxy)phenyl]-1-(2-chlorobenzyl)-2-thiourea

3-[3'-(N'-methylcarbamoyloxy)phenyl]-1-(4-chlorobenzyl)-2-thiourea

3-[3'-(N'-methylcarbamoyloxy)phenyl]-1-(1-naphthyl)-2-thiourea

3-[3'-(N'-methylcarbamoyloxy)phenyl]-1,1-di-n-octyl-2-thiourea

3-[3'-(N'-methylcarbamoyloxy)phenyl]-1-(2-chloroallyl)-1-dodecyl-2-thiourea

3-[3'-(N'-methylcarbamoyloxy)phenyl]-1-phenyl-1-(alpha-methylbenzyl)-2-thiourea

3-[3'-(N'-methylcarbamoyloxy)phenyl]-1-(1,1,3,3-tetramethylbutyl)-2-thiourea

3-[3'-(N'-methylcarbamoyloxy)phenyl]-1-methyl-1-(2-chloroallyl)-2-thiourea

3-[3'-(N'-methylcarbamoyloxy)phenyl]-1,1-dipropargyl-2-thiourea

3-[3'-(N'-methylcarbamoyloxy)phenyl]-1-propargyl-1-benzyl-2-thiourea

3-[3'-(N'-methylcarbamoyloxy)phenyl]-1-methyl-1-octadecyl-2-thiourea

3-[3'-(N',N'-dimethylcarbamoyloxy)phenyl]-1-methyl-1-(2-chloroallyl)-2-thiourea

3-[3'-(N',N'-diethylcarbamoyloxy)phenyl]-1-methyl-1-(2-chloroallyl)-2-thiourea

3-[3'-(N'-methyl-N'-n-butylcarbamoyloxy)phenyl]-1-methyl-1-(2-chloroallyl)-2-thiourea

3-[3'-(N'-1-pyrolidylcarbamoyloxy)phenyl]-1-methyl-1-(2-chloroallyl)-2-thiourea

3-(3'-(N,N'-di-n-butylcarbamoyloxy)phenyl]-1-methyl-1-(2-chloroallyl)-2-thiourea

3-[3'-(N'-methyl-N'-benzylcarbamoyloxy)phenyl]-1-methyl-1-(2-chloroallyl)-2-thiourea

3-[3'-(N'-t-butylcarbamoyloxy)phenyl]-1-methyl-1-(2-chloroallyl)-2-thiourea

3-[3'-(N'-n-butylcarbamoyloxy)phenyl]-1-methyl-1-(2-chloroallyl)-2-thiourea

3-[3'-(N'-allylcarbamoyloxy)phenyl]-1-methyl-1-(2-chloroallyl)-2-thiourea

3-[3'-(N'-cyclohexylcarbamoyloxy)phenyl]-1-methyl-1-(2-chloroallyl)-2-thiourea

3-[3'-(N'-alpha-methylbenzylcarbamoyloxy]-1-methyl-1-(2-chloroallyl)-2-thiourea

3-[3'-(N'-phenylcarbamoyloxy)phenyl]-1-methyl-1-(2-chloroallyl)-2-thiourea

3-[3'-(N'-3-chlorophenyl)phenyl]-1-methyl-1-(2-chloroallyl)-2-thiourea

3-[3'-(N'-methylcarbamoyloxy)phenyl]-1-methyl-1-cyclododecyl-2-thiourea

3-[3'-(N'-methylcarbamoyloxy)phenyl]-1-methyl-1-(2-phenylethyl)-2-thiourea

3'[3'-(N'-methylcarbamoyloxy)phenyl]-1-(1,1-dimethyl-2-phenylethyl)-2-thiourea

3-[3'-(N'-methylcarbamoyloxy)phenyl]-1-methyl-1-naphthyl-2-thiourea

3-[3'-(N'-methylcarbamoyloxy(phenyl]-1-methyl-1-(1-naphthylmethyl)-2-thiourea

3-[3'-(N'-methylcarbamoyloxy)phenyl]-1-(alphaisopropylbenzyl)-2-thiourea

3-[3'-(N'-methylcarbamoyloxy)phenyl]-1-(alpha-t-butyl-4-methoxybenzyl)-2-thiourea

3-[3'-(N'-1-pyrrolidylcarbamoyloxy)phenyl]-1-methyl-1-(1-naphthylmethyl)-2-thiourea

3-[3'-(N',N'-dimethylcarbamoyloxy)phenyl]-1-methyl-1-(1-naphthylmethyl)-2-thiourea

3-[3'-(N'-methyl-N'-2-chlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3'[3'-(N'-ethyl-N'-4-chlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-t-butylcarbamoyloxy)phenyl)]-1-isopropyl-1-(2-phenethyl)urea

3-[3'-(N'-allyl-N'-2-phenylethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-4-chlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-alphamethyl-4-chlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-alpha ethylbenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-alpha isopropylbenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-4-methylbenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-t-butylcarbamoyloxy)phenyl]-1-methyl-1-benzylurea

3-[3'-(N'-benzylcarbamoyloxy)phenyl]-1-methyl-1-benzylurea

3-[3'-(N'-cyclohexylcarbamoyloxy)phenyl]-1-methyl-1-benzylurea

3-[3'-(N'-phenylcarbamoyloxy)phenyl]-1-methyl-1-benzylurea

3-[3'-(N'-methylcarbamoyloxy)phenyl]-1-methyl-1-benzylurea

3-[3'-(N'-methyl-N'-benzylcarbamoyloxy)phenyl]-1-methyl-2-thiourea

3-[3'-(N'-methylcarbamoyloxy)phenyl]-1-allyl-2-thiourea

3-[3'-(N'-methyl-N'-2-(2-methyl-4-chlorophenoxy)ethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-alpha,4-dimethylbenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-1,1-dimethyl-2-phenethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-methyl-N'-alpha,4-dimethylbenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-alphaisopropyl-4-methoxybenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-alpha-n-propylbenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-diphenylmethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-2-(3-chlorophenoxy)ethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-2-(1-naphthoxy)ethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-2-(2-naphthoxy)ethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-2-(4-chlorophenoxy)ethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-methyl-N'-2-(3-chlorophenoxy)ethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-benzylthiocarbamoylthiol)phenyl]-1,1-dimthylurea

3-[3'-(N'-allyl-N'-2,6-dichlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-isopropyl-N'-2,6-dichlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-isopropyl-N'-2-chlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea.

3-[3'-(N'-allyl-N'-2-chlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-N'-allyl-N'-4-chlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-allyl-N'-2,4-dichlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-allyl-N'-2,6-dichlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-allyl-N'-alpha-methylphenethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-allyl-N'-phenethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-allyl-N'-benzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-butyl-N'-2-chlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-tert.butyl-N'-2-chlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-tert.butyl-N'-4-chlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-sec.butyl-N'-4-chlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-tert.butyl-N'-2,4-dichlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-cyclohexyl-N'-4-chlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-2-chloroallyl-N'-benzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-methyl-N'-2-(4-chloro-2-methylphenoxy)ethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-methyl-N'-2-(2-chlorophenoxy)ethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-methyl-N'-2-(3-chlorophenoxy)ethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-methyl-N'-2-(4-chlorophenoxy)ethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-methyl-N'-2-(2,4-dichlorophenoxy)ethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-methyl-N'-2-(1-naphthoxy)ethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-isopropyl-N'-2-(1-naphthoxy)ethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-methyl-N'-2-(2-naphthoxy)ethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-methyl-N'-4-phenoxybutylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-methyl-N'-2-phenoxyethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-methyl-N'-3-phenoxypropylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-2,3-dichloroallyl-N'-benzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-methyl-N'-3,4-dichlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-methyl-N'-alpha-methylbenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-1,3-dimethylbutyl-N'-4-chlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-1,3-dimethylbutyl-N'-2,4-dichlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-methyl-N'-alpha-methyl-4-chlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-methyl-N'-alpha-methylphenethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-ethyl-N'-1-naphthylmethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-methyl-N'-2-fluorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-methyl-N'-alpha-methylene-2,4,6-trimethylbenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-2,2,3-trichloroallyl-N'-benzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-4-bromo-alpha-methylbenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-alpha-tert.butyl-4-methoxybenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-2-(4-chloro-2-methylphenoxy)ethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-5-(2-chlorophenoxy)pentylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-2-(4-chloro-2,5-xylyloxy)ethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-2-(4-chloro-3,5-xylyloxy)ethylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-2,2-dimethyl-3-phenylpropylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-alpha-methyl-3-methoxybenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-alpha-methyl-3,4-dichlorobenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

3-[3'-(N'-alpha,2,4-trimethylbenzylcarbamoyloxy)phenyl]-1,1-dimethylurea

The following urea-carbanilates were also prepared by substantially thesame procedure as previously shown. Sulfur analogs of the carbanilategroup will be represented as follows: ##STR27##

The nitrogen of the urea group attached to the metabifunctional phenylring will be the "3" nitrogen and the other nitrogen the "1" nitrogen.

methyl ester m-[3-(1-ethyl)-2-thioureido]dithiocarbanilic acid

ethyl ester m-[3-(1-ethyl)-2-thioureido]carbanilic acid

ethyl ester m-[3-(1-phenyl)-2-thioureido]carbanilic acid

methyl ester m-[3-(1-ethyl)-2-thioureido]carbanilic acid

methyl ester m-[3-(1-t-butyl)-2-thioureido]-thiolcarbanilic acid

methyl ester m-[3-(1-(4'-phenoxy)phenyl)-2-thioureido]carbanilic acid

methyl ester m-[3-(1-3'-methylthio)phenyl)ureido]carbanilic acid

phenyl ester m-[3-(1-(3'-methylthio)phenyl)ureido]carbanilic acid

isopropyl ester m-[3-(1-(3'-methylthio)phenyl)ureido]carbanilic acid

methyl ester m-[3-(1-(3'-trifluoromethyl)phenyl)ureido]carbanilic acid

isoproyl ester m-[3-(1-(3'-trifluoromethyl)phenyl)ureido]carbanilic acid

phenyl ester m-[3-(1-(3'-trifluoromethyl)phenyl)ureido]carbanilic acid

methyl ester m-[3-(1-(3'-methylthio)phenyl)thioureido]carbanilic acid

methyl ester m-[3-(1-(3'-trifluoromethyl)phenyl)thioureido]carbanilicacid

phenyl ester m-[3-(1-(3'-trifluoromethyl)phenyl)thioureido]carbanilicacid

phenyl ester m-[3-(1-(3'-methylthio)phenyl)thioureido]carbanilic acid

phenyl ester m-[3'-(1-(3'-fluoro)phenyl)thioureido]carbanilic acid

methyl ester m-[3-(1,1-dimethyl)ureido]-thiolcarbanilic acid

isopropyl ester m-[3-(1-allyl)thioureido]carbanilic acid

isopropyl ester m-[3-(1-phenyl)thioureido]carbanilic acid

ethyl ester m-[3-(1,1-dimethyl)ureido]thiolcarbanilic acid

ethyl ester m-[3-(1,1-piperidyl)ureido]thiolcarbanilic acid

methyl ester m-[3-(1-t-butyl)thioureido]carbanilic acid

methyl ester m-[3-(1,1-piperidyl)thioureido]carbanilic acid

methyl ester m-[3-(1,1-di-isopropyl)thioureido]carbanilic acid

methyl ester m-[3-(1,1-diethyl)thioureido]carbanilic acid

methyl ester m-[3-(1,1-diallyl)thioureido]carbanilic acid

isopropyl ester m-[3-(1-t-butyl)thioureido]carbanilic acid

methyl ester m-[3-(1-t-butyl)ureido]carbanilic acid

methyl ester m-[3-(1-methyl)ureido]carbanilic acid

The following di-urea compounds were prepared by substantially the sameprocedure as previously shown.

1-methyl-3-[3'-(1-(3",4"-dichloro)phenyl)ureido]phenylthiourea

1-ethyl-3-[3'-(1-(3",4"-dichloro)phenyl)thioureido]phenylthiourea

1,1-dimethyl-3-[3'-(1-(2-chloroallyl)thioureido]phenylurea

1,1-dimethyl-3-[3'-(1-(3",4"-dichloro)phenyl)thiourea]phenylurea

1,1-dimethyl-3-[3'-(1-allyl)thioureido]phenylurea

1-t-butyl-3-[3'-(1,1-dimethyl)ureido]phenylthiourea

1-(2-chloroallyl)-1-methyl-3-[3'-(1,1-dimethyl)ureido]phenylthiourea

1,1-dimethyl-3-[3'-(1-(2-phenoxy)ethyl)ureido]phenylurea

1,1-dimethyl-3-[3'-(1-(2-o-chlorophenoxy)ethyl]ureido]phenylurea

In accordance with this invention it has been found that the growth ofdormant seeds, germinant seeds, germinative seeds, emerging seedlingsand established woody and herbaceous vegetation can be modified byexposing the seeds, emerging seedlings, or the roots or above-groundportions of established vegetation, to the action of an effective amountof the compounds of the present invention. The compounds can be used asindividual compounds, as admixtures of two or more compounds, or inadmixture with an adjuvant. These compounds are effective aspost-emergent herbicides and pre-emergent herbicides, but their mostoutstanding utility is as selective pre-emergent and post-emergentactivity, e.g. the selective control of the growth of one or moremonocotyledonous species and/or one or more dicotyledonous species inthe presence of other monocotyledons and/or dicotyledons. Furthermore,these compounds are characterized by broad spectrum activity; i.e. theymodify the growth of a wide variety of plants.

For the sake of brevity and simplicity, the term "active ingredient"will be used hereinafter to describe the present 3'-(carbamoyloxy)ureas;ureidoureas and ureacarbanilates.

The herbicidal compositions of this invention contain at least oneactive ingredient and an adjuvant in liquid or solid form. Thecompositions are prepared by admixing the active ingredient with anadjuvant including diluents, extenders, carriers and conditioning agentsto provide compositions in the form of finely-divided particulatesolids, granules, pellets, solutions, dispersions or emulsions. Thus theactive ingredient can be used with an adjuvant such as a finely-dividedsolid, a liquid of organic origin, water, a wetting agent, a dispersingagent, an emulsifying agent or any suitable combination of these.

The term "herbicidal composition" as used herein and in the appendedclaims is intended to mean not only compositions in a suitable form forapplication but also concentrated compositions which require dilution orextension with a suitable quantity of liquid or solid adjuvant prior toapplication.

The pre-emergent herbicidal activity of illustrative compounds of thisinvention is demonstrated as follows.

A good grade of top soil is placed in aluminum pans and compacted to adepth of 3/8" to 1/2" from the top of each pan. A predetermined numberof seeds of each various plant species are placed on top of the soil ineach pan. The herbicidal compositions are applied to the soil byadmixture with or incorporation in the top soil layer.

In the surface application method the seeds are covered with a 3/8"layer of prepared soil and the pan leveled. The herbicidal compositionis applied by spraying the surface of the top layer of soil, prior towatering the seeds, with a solution containing a sufficient amount ofactive ingredient to obtain the desired rate per acre on the soilsurface.

In the soil incorporation method, the soil required to cover the seedsis weighed and admixed with a herbicidal composition containing a knownamount of active ingredient. The pans are then filled with the admixtureand leveled. Watering is carried out by permitting the soil in the pansto absorb moisture through the apertured bottom of the pans. The seedcontaining pans are placed on a sand bench and maintained forapproximately 14 or 28 days under ordinary conditions of sunlight andwatering. The plants are observed at the end of approximately 14 or 28days and the results recorded.

The pre-emergent herbicidal activity of the active ingredients ismeasured by the average percent control of each seed lot. The averagepercent control is converted to a relative numerical scale for the sakeof brevity and simplicity in the examples. The pre-emergent herbicidalactivity index used in the Tables is defined as follows:

    ______________________________________                                        Average Percent            Numerical                                          Control                    Scale                                              ______________________________________                                         0-25      =               0                                                  26-50      =               1                                                  51-75      =               2                                                   76-100    =               3                                                  ______________________________________                                    

The pre-emergent herbicidal activity of some of the3'-(carbamoyloxy)ureas of this invention is recorded in Table I forvarious application rates of the active ingredients. The data recordedin Table I is observation after 14 days unless otherwise indicated.

    TABLE I      PRE-EMERGENT HERBICIDAL ACTIVITY  Rate               Barn-   Morn-     Yellow   Wild  Com- lb/ Sugar Cot- Soy-    Pig- Smart- Cockle- Lambs-     Hemp Velvet Wild Brome yard Crab Canada ing Nut- Quack Johnson Buck-     Pani- pound acre Beet ton bean Corn Wheat Rice weed weed bur quarter     Sesbania Leaf Oat Grass Grass Grass Thistle Glory sedge Grass Grass     wheat cum       I 1 2 0 0 0 0 1 3 0 0 1 3 2 0 00 0 -- -- -- -- -- -- -- II 1 -- -- --     -- -- -- -- 3 2 1 -- 3 -- 0 2 -- 0 1 1 2 0 -- --  III 1 3 -- 0 -- 0 0 --     3 0 3 2 3 -- 0 1 3 -- 0 -- -- -- 1 0 IV 5 -- -- -- -- -- -- -- 2 1 3 --     1 -- 1 0-- 1 2 0 0 1 -- -- V 1 3 -- 1 -- 0 0 -- 3 1 2 3 3 -- 0 2 2 -- 3     -- -- -- 1 0 VI 2 2 0 0 1 0 1 1 1 1 1 1 0 1 0 1 2 -- -- -- -- -- -- --     VII 1 1 2 0 0 0 0 3 2 0 3 1 0 0 0 0 0 -- -- -- -- -- -- --VIII 2 3 2 0 0     0 0 3 0 0 3 1 2 1 0 1 2 -- -- -- -- -- -- --     Compound     I 3[3(Nalpha methylbenzylcarbamoyloxy)phenyl1,1-dimethylurea     II 3[3(Nalpha-n-propylbenzylcarbamoyloxy)phenyl1,1-dimethylurea     III 3[3(N(1,1-dimethyl-2-phenylethylcarbamoyloxy)phenyl1,1-dimethylurea     IV 3[3(Nmethylcarbamoyloxy)phenyl1-allylthiourea     V 3[3(Nalpha methyl4-chlorobenzylcarbamoyloxy)phenyl1,1-dimethylurea     VI ethyl N[3(1,1-dimethyl)ureido]thiolcarbanilate     VII phenyl N[3(1-m-trifluoromethylphenyl)ureido]carbanilate     VIII 1t-butyl-3-[3(1,1-dimethyl)ureido]phenylthiourea

Although the compounds of this invention possess pre-emergent activity,they are more active as post-emergent herbicides. This is illustrated bythe following.

The active ingredients are applied in spray form to 14-day or 21 day oldplants species. The spray, an organic solvent-water solution containingthe active ingredient, is applied to the plants in different set of pansat defined rates per acre. The treated plants are placed in a greenhouseand the effects observed and recorded after approximately 14 days orapproximately 28 days. The data recorded in Tables II, III and IV is for14 day observations on 21 day old specimen unless otherwise indicated.

The post-emergent herbicidal activity index used in Tables II, III andIV is measured by the average percent control of each plant species andis defined as follows:

    ______________________________________                                        Average Percent    Numerical                                                  Control            Scale                                                      ______________________________________                                         0-25              0                                                          26-50              1                                                          51-75              2                                                          76-99              3                                                          100                4                                                          ______________________________________                                    

                                      TABLE II                                    __________________________________________________________________________    POST-EMERGENT HERBICIDAL DATA-CARBAMOYLOXY-UREAS                                                                                 John-   Barn-              Com-                                                                              %   Canada                                                                            Cockle-     Morning           Yellow                                                                             Quack                                                                             son Brome                                                                             yard               pounds                                                                            Conc                                                                              Thistle                                                                           bur  Velvet Leaf                                                                          Glory                                                                              Lambsquarter                                                                         Smartweed                                                                           Nutsedge                                                                           Grass                                                                             Grass                                                                             Grass                                                                             Grass              __________________________________________________________________________    I   0.2 2   4    4      4    4      4     0    4   0   2   2                  II  0.2 0   3    2      3    4      4     0    1   1   1   2                  III 0.2 1   3    1      2    3      2     0    1   0   1   2                  IV  0.2 (a)                                                                           4   4    4      4    4      --    0    1   --  1   2                  V   0.2 (a)                                                                           --  4    3      4    4      4     1    2   0   1   2                  __________________________________________________________________________     (a) active ingredient applied to 14 day old plant specimen                    Compound I                                                                    1,1dimethyl-3-[3(Nmethyl-N2-m-chlorophenoxyethylcarbamoyloxy)phenyl] urea     Compound II  1,1dimethyl-3-[3(N1,1-dimethyl-2-phenylcarbamoyloxy)phenyl]      urea                                                                          Compound III                                                                  1,1dimethyl-3-[3(Nmethyl-N2-(2-methyl-4-chlorophenyl)ethylcarbamoyloxy)ph    nyl] urea                                                                      Compound IV  1,1dimethyl-3-[3(N4-methylbenzylcarbamoyloxy)phenyl] urea        Compound V  1,1dimethyl-3-[3(Nalpha isopropylbenzylcarbamoyloxy)phenyl]       urea                                                                     

                                      TABLE III                                   __________________________________________________________________________    POST-EMERGENT HERBICIDAL ACTIVITY-UREA-CARBANILATES                                  Sug-                      Coc-        Vel-      Barn-                  Com-                                                                              %  ar Cot-                                                                             Soy-         Pig-                                                                             Smart-                                                                            kle-                                                                             Lambs-                                                                            Hemp vet                                                                              Wild                                                                             Brome                                                                             yard                                                                              Crab               pound                                                                             Conc                                                                             Beet                                                                             ton                                                                              bean                                                                             Corn                                                                             Wheat                                                                             Rice                                                                             weed                                                                             weed                                                                              bur                                                                              quarter                                                                           Sesbania                                                                           Leaf                                                                             Oat                                                                              Grass                                                                             Grass                                                                             Grass              __________________________________________________________________________    I   0.2                                                                              3  2  3  0  0   3  3  4   3  4   4    0  1  1   1   3                  II  0.2                                                                              3  0  1  1  0   0  4  4   0  4   4    2  1  1   2   3                  III 0.2                                                                              4  1  3  1  0   0  4  4   1  3   4    2  1  2   3   2                  __________________________________________________________________________     Compound I  methyl N[3(1-t-butylureido)]thiolcarbanilate                      Compound II  methyl N[3(1-(4-phenoxy)phenylthioureido)]carbanilate            Compound III  methyl N[3(1-t-butylthioureido)]carbanilate                

                                      TABLE IV                                    __________________________________________________________________________    POST-EMERGENT HERBICIDAL ACTIVITY-DI-UREAS                                            Sug-                      Coc-   Hemp                                                                              Vel-      Barn-                  Com-                                                                              %   ar Cot-                                                                             Soy-         Pig-                                                                             Smart-                                                                            kle-                                                                             Lambs-                                                                            ses-                                                                              vet                                                                              Wild                                                                             Brome                                                                             yard                                                                              Crab               pound                                                                             Conc                                                                              Beet                                                                             ton                                                                              bean                                                                             Corn                                                                             Wheat                                                                             Rice                                                                             weed                                                                             weed                                                                              bur                                                                              quarter                                                                           bania                                                                             Leaf                                                                             oats                                                                             Grass                                                                             Grass                                                                             Grass              __________________________________________________________________________    I   0.05                                                                              4  1  3  1  1   1  4  4   3  4   3   2  2  2   2   3                  II  0.05 (a)                                                                          3  1  1  1  2   3  4  2   1  3   3   1  1  2   2   2                  III 0.05                                                                              4  2  1  1  1   2  4  4   4  4   4   2  1  1   2   3                  IV  0.01                                                                              4  2  1  0  0   0  4  3   0  4   4   1  0  1   0   1                  __________________________________________________________________________     Compound I  1,1dimethyl-3-[3(1-(2-chloroallyl)thioureido)phenyl] urea         Compound II  1,1dimethyl-3-[3(1-(3,4-dichlorophenyl)thioureido)phenyl]        urea                                                                          Compound III  1t-butyl-3-[3(1,1-dimethylureido)phenyl] urea                   Compound IV  1methyl-1-(2-chloroallyl)-3-[3(1,1-dimethylureido)phenyl]        thiourea                                                                 

In addition to the general herbicidal activity of the compounds of thisinvention, they also exhibit selective activity on weeds in the presenceof crops.

As mentioned hereinbefore the herbicidal compositions of this inventioncomprise an active ingredient and one or more adjuvants which can besolid or liquid extenders, carriers, diluents, conditioning agents andthe like. Preferred herbicidal compositions containing the activeingredients of this invention have been developed so that the activeingredients can be used to the greatest advantage to modify the growthof plants. The preferred compositions comprise wettable powders, aqueoussuspensions, dust formulations, granules, emulsifiable oils andsolutions in solvents. In general, these preferred compositions can allcontain one or more surface-active agents.

Surface-active agents which can be used in the phytotoxic compositionsof this invention are set out, for example, in Searle U.S. Pat. No.2,426,417, Todd U.S. Pat. No. 2,655,447, Jones U.S. Pat. No. 2,412,510and Lenher U.S. Pat. No. 2,139,276. A detailed list of such agents isalso set forth by J. W. McCutcheon in "Soap and Chemical Specialties",November 1947, page 8011 et seq., entitled "Synthetic Detergents";"Detergents and Emulsifiers--Up to Date" (1960), by J. W. McCutcheon,Inc., and Bulletin E-607 of the Bureau of Entomology and PlantQuarantine of the U.S.D.A. In general, less than 50 parts by weight ofthe surface active agent is present per 100 parts by weight of theherbicidal composition.

Wettable powders are water-dispersible compositions containing one ormore active ingredients, an inert solid extender and one or more wettingand dispersing agents. The inert solid extenders are usually of mineralorigin such as the natural clays, diatomaceous earth and syntheticminerals derived from silica and the like. Examples of such extendersinclude kaolinites, attapulgite clay and synthetic magnesium silicate.Preferred wetting agents are alkyl benzene and alkyl naphthalenesulfonates, sulfated fatty alcohols, amines or acid amides, long chainacid esters of sodium isothionate, esters of sodium sulfosuccinate,sulfated or sulfonated fatty acid esters, petroleum sulfonates,sulfonated vegetable oils, ditertiary acetylinic glycols,polyoxyethylene derivatives of alkylphenols (particularly isooctylphenoland nonylphenol) and polyoxyethylene derivatives of the mono-higherfatty acid esters of hexitol anhydrides (e.g. sorbitan). Preferreddispersants are methyl cellulose, polyvinyl alcohol, sodium ligninsulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalenesulfonate, polymethylene bisnaphthalenesulfonate and sodiumN-methyl-N-(long chain acid) taurates.

The wettable powders compositions of this invention usually contain fromabout 5 to about 95 parts by weight of active ingredient, from about0.25 to 25 parts by weight of wetting agent, from about 0.25 to 25 partsby weight of dispersant and from 4.5 to about 94.5 parts by weight ofinert solid extender, all parts being by weight of the totalcomposition. Where required from about 0.1 to 2.0 parts by weight of thesolid inert extender can be replaced by a corrosion inhibitor orantifoaming agent or both.

Aqueous suspensions can be prepared by mixing together and grinding anaqueous slurry of water-insoluble active ingredient in the presence ofdispersing agents to obtain a concentrated slurry of very finely-dividedparticles. The resulting concentrated aqueous suspension ischaracterized by its extremely small particle size, so that when dilutedand sprayed coverage is very uniform.

Dusts are dense finely-divided particulate compositions which areintended for application to the soil in dry form. Dusts arecharacterized by their free-flowing and rapid settling properties sothat they are not readily wind-borne to areas where they are of novalue. Dusts contain primarily an active ingredient and a dense,free-flowing finely-divided particulate extender. However, theirperformance is sometimes aided by the inclusion of a wetting agent suchas those listed hereinbefore under wettable powder compositions andconvenience in manufacture frequently demands the inclusion of an inert,absorptive grinding aid. Suitable classes of grinding aids are naturalclays, diatomaceous earth and synthetic minerals derived from silica orsilicate. Preferred grinding aids include attapulgite clay, diatomaceoussilica, synthetic fine silica and synthetic calcium and magnesiumsilicates.

The inert finely-divided solid extender for the dusts can be either ofvegetable or mineral origin. The solid extenders are characterized bypossessing relatively low surface areas and are poor in liquidabsorption. Suitable inert solid extenders for plant growth regulantdusts include micaceous talcs, pyrophyllite, dense kaolin clays, groundcalcium phosphate rock and tobacco dust. The dusts usually contain fromabout 0.5 to 95 parts active ingredient, 0 to 50 parts grinding aid, 0to 50 parts wetting agent and 5 to 99.5 parts dense solid extender, allparts being by weight and based on the total weight of the dust.

The wettable powders described above may also be used in the preparationof dusts. While such wettable powders could be used directly in dustform, it is more advantageous to dilute them by blending with the densedust diluent. In this manner, dispersing agents, corrosion inhibitors,and anti-foam agents may also be bound as components of a dust.

Emulsifiable oils are usually solutions of active ingredient inwater-immiscible or partially water-immiscible solvents together with asurface active agent. Suitable solvents for the active ingredient ofthis invention include hydrocarbons and water-immiscible ethers, estersor ketones. Suitable surface active agents are anionic, cationic andnon-ionic such as alkyl aryl polyethoxy alcohols, polyethylene sorbitolor sorbitan fatty acid esters, polyethylene glycol fatty esters, fattyalkyllol amide condensates, amine salts of fatty alcohol sulfatestogether with long chain alcohols and oil soluble petroleum sulfonatesor mixtures thereof. The emulsifiable oil compositions generally containfrom about 5 to 95 parts active ingredient, about 1 to 50 parts surfaceactive agent and about 4 to 94 parts solvent, all parts being by weightbased on the total weight of emulsifiable oil.

Granules are physically stable particulate compositions comprisingactive ingredient adhering to or distributed through a basic matrix ofan inert, finely-divided particulate extender. In order to aid leachingof the active ingredient from the particulate, a surface active agentsuch as those listed hereinbefore under wettable powders can be presentin the composition. Natural clays, pyrophyllites, illite and vermiculiteare examples of operable classes of particulate mineral extenders. Thepreferred extenders are the porous, absorptive, preformed particles suchas preformed and screened particulate attapulgite or heat expanded,particulate vermiculite, and the finely-divided clays such as kaolinclays, hydrated attapulgite or bentonitic clays. These extenders aresprayed or blended with the active ingredient to form the herbicidalgranules.

The mineral particles which are used in the granular herbicidalcompositions of this invention usually have a size range of 10 to 100mesh, but preferably such that a large majority of the particles havefrom 14 to 60 mesh with the optimum size being from 20 to 40 mesh. Clayhaving substantially all particles between 14 and 80 mesh and at leastabout 80 percent between 20 and 40 mesh is particularly preferred foruse in the present granular composition. The term "mesh" as used hereinmeans U.S. Sieve Series.

The granular herbicidal compositions of this invention generally containfrom about 5 parts to about 30 parts by weight of active ingredient per100 parts by weight of clay and 0 to about 5 parts by weight of surfaceactive agent per 100 parts by weight of particulate clay. The preferredherbicidal granular compositions contain from about 10 parts to about 25parts by weight of active ingredient per 100 parts by weight of clay.

The herbicidal compositions of this invention can also contain otheradditaments, for example fertilizers, phytotoxicants, other plant growthregulants, pesticides and the like used as adjuvant or in combinationwith any of the above-described adjuvants. Chemicals useful incombination with the active ingredients of this invention include forexample triazines, ureas, carbamates, acetamides, acetanilides, uracils,acetic acids, phenols, thiolcarbamates, triazoles, benzoic acids,nitriles and the like such as:

3-amino-2,5-dichlorobenzoic acid

3-amino-1,2,4-triazole

2-methoxy-4-ethylamino-6-isopropylamino-s-triazine

2-chloro-4-ethylamino-6-isopropylamino-s-triazine

2-chloro-N,N-diallylacetamide

2-chloroallyl diethyldithiocarbamate

N'-(4-chlorophenoxy) phenyl-N,N-dimethylurea

isopropyl M-(3-chlorophenyl)carbamate

2,2-dichloropropionic acid

S-2,3-dichloroallyl N,N-diisopropylthiolcarbamate

2-methoxy-3,6-dichlorobenzoic acid

2,6-dichlorobenzonitrile

6,7-dihydrodipyrido(1,2-a:2',1'-c)-pyrazidiinium salt

3-(3,4-dichlorophenyl)-1,1-dimethylurea

4,6-dinitro-o-sec-butylphenol

2-methyl-4,6-dinitrophenol

ethyl N, N-dipropylthiolcarbamate

2,3,6-trichlorophenylacetic acid

3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea

2-methyl-4-chlorophenoxyacetic acid

3-(p-chlorophenyl)-1,1-dimethylurea

1-butyl-3-(3,4-dichlorophenyl)-1-methylurea

N-1-naphthylphthalamic acid

1,1'-dimethyl-4,4'-bipyridinium salt

2-chloro-4,6-bis(isopropylamino)-s-triazine

2-chloro-4,6-bis(ethylamino)-s-triazine

2,4-dichlorophenyl-4-nitrophenyl ether

alpha,alpha,alpha-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine

S-propyl dipropylthiolcarbamate

2,4-dichlorophenoxyacetic acid

2',6'-diethyl-N-methoxymethyl-2-chloroacetanilide

Fertilizers useful in combination with the active ingredients includefor example ammonium nitrate, urea, potash, and superphosphate. Otheruseful additaments include materials in which plant organisms take rootand grow such as compost, manure, humus, sand and the like.

When operating in accordance with the present invention, effectiveamounts of the active ingredient are dispersed in or on soil or plantgrowth media and/or applied to above-ground portions of plants, in anyconvenient fashion. Application to the soil or growth media can becarried out by simply admixing with the soil, by applying to the surfaceof the soil and thereafter dragging or discing into the soil to thedesired depth, or by employing a liquid carrier to accomplish thepenetration and impregnation. The application of liquid and particulatesolid herbicidal compositions to the surface of soil or to above-groundportions of plants can be carried out by conventional methods, e.g.power dusters, boom and hand sprayers and spray dusters. Thecompositions can also be applied from airplanes as a dust or a spraybecause of their effectiveness at low dosages. In a further method, thedistribution of the active ingredients in soil can be carried out byadmixture with the water employed to irrigate the soil. In suchprocedures, the amount of water can be varied with the porosity andwater holding capacity of the soil to obtain the desired depth ofdistribution of the herbicide.

The application of an effective amount of the compounds of thisinvention to the soil or growth media and/or plant is essential andcritical for the practice of one embodiment of the present invention.The exact amount of active ingredient to be employed is dependent uponthe response desired in the plant as well as such other factors as theplant species and stage of development thereof, the specific soil anddepth at which the active ingredients are distributed in the soil andthe amount of rainfall as well as the specific active ingredientemployed. In foliar treatment for the modification of vegetative growth,the active ingredients are applied in amounts from about 0.001 to about25 or more pounds per acre. In applications to soil for the modificationof the growth of germinant seeds, germinative seeds, emerging seedlingsand established vegetation, the active ingredients are applied inamounts from about 0.1 to about 50 or more pounds per acre. In such soilapplications, it is desirable that the active ingredients be distributedto a depth of at least 0.2 inches. In selective pre-emergence herbicidalapplications the active ingredients are usually applied in amounts fromabout 0.1 to 5 pounds per acre. It is believed that one skilled in theart can readily determine from the teachings of this specification,including examples, the approximate application rate for any situation.

The terms "soil" and "growth media" are employed in the presentspecification and claims in their broadest sense to be inclusive of allconventional "soils" as defined in Webster's New InternationalDictionary, Second Edition, Unabridged (1961). Thus, the terms refer toany substance or media in which vegetation may take root and grow, andare intended to include not only earth but also compost, manure, muck,humus, sand and the like, adapted to support plant growth.

Although the invention is described with respect to specificmodifications, the details thereof are not to be construed aslimitations except to the extent indicated in the following claims.

What is claimed is:
 1. A meta-bifunctional substituted benzene havingthe formula ##STR28## wherein R' is selected from the group consistingof hydrogen and alkyl having a maximum of 8 carbon atoms; R² is alkylhaving a maximum of 12 carbon atoms; R³ is selected from the groupconsisting of hydrogen and alkyl having a maximum of 12 carbon atoms;R¹² is selected from the group consisting of hydrogen, alkyl having amaximum of 6 carbon atoms; and R¹³ is selected from the group consistingof alkyl having a maximum of 8 carbon atoms.
 2. A meta-bifunctionalsubstituted benzene according to claim 1 in which R¹ and R¹² are eachindependently selected from the group consisting of hydrogen and alkylhaving a maximum of 4 carbon atoms.
 3. A meta-bifunctional substitutedbenzene according to claim 2 in which R¹ and R¹² are both hydrogen.
 4. Acompound having the formula ##STR29## in which R' is alkyl containingfrom one to eight carbon atoms, inclusive, or benzyl and R² is alkylhaving a maximum of 12 carbon atoms and R³ is selected from the groupconsisting of hydrogen and alkyl having a maximum of 12 carbon atoms,inclusive.
 5. A compound according to claim 4 wherein R' is alkyl, R² isalkyl and R³ is hydrogen.
 6. A compound according to claim 5 wherein R²is methyl.
 7. A compound according to claim 4 wherein R' is alkyl, R² isalkyl and R³ is alkyl.
 8. A herbicidal composition comprising aherbicidally inert adjuvant and a herbicidally effective amount of ameta-bifunctional substituted benzene of the formula ##STR30## whereinR' is selected from the group consisting of hydrogen, alkyl having amaximum of 8 carbon atoms; R² is alkyl having a maximum of 12 carbonatoms; R³ is selected from the group consisting of hydrogen and alkylhaving a maximum of 12 carbon atoms; R¹² is selected from the groupconsisting of hydrogen, alkyl having a maximum of 6 carbon atoms; andR¹³ is selected from the group consisting of alkyl having a maximum of 8carbon atoms.
 9. A herbicidal composition according to claim 8 in whichR' and R¹² are each independently selected from the group consisting ofhydrogen and alkyl having a maximum of 4 carbon atoms.
 10. A herbicidalcomposition according to claim 9 in which R' and R¹² are both hydrogen.11. A herbicidal method which comprises applying to plants a herbicidaleffective amount of a meta-bifunctional substituted benzene of theformula ##STR31## wherein R' is selected from the group consisting ofhydrogen, alkyl having a maximum of 8 carbon atoms; R² is alkyl having amaximum of 12 carbon atoms; R³ is selected from the group consisting ofhydrogen and alkyl having a maximum of 12 carbon atoms; R¹² is selectedfrom the group consisting of hydrogen, alkyl having a maximum of 6carbon atoms; and R¹³ is selected from the group consisting of alkylhaving a maximum of 8 carbon atoms.
 12. A herbicidal method according toclaim 11 in which R' and R¹² are each independently selected from thegroup consisting of hydrogen and alkyl having a maximum of 4 carbonatoms.
 13. A herbicidal method according to claim 12 in which R' and R¹²are both hydrogen.